Amino-methylene derivatives of salicylamide and process therefor



Patented Oct. 2, 1945 UNITED STATE AMINO-METHYLENE DERIVATIVES F SALI- CYLAMIDE- AND PROCESS THEREFOR Donald Price, New York,

Bond, Cranford, N.

' Oil Products Company, Harrison,

poration of New Jersey No Drawing. Application July 15, 1943,

Serial No. 494,854

9 Claims.

This invention relates to novel higher fatty salicylic derivatives and to a method for preparing the same.

Various derivatives of parahydroxy benzoic acid have been condensed with formaldehyde and primary and secondary amines, amino methylene derivatives apparently being formed during the reaction. This reaction has not, however, hitherto been found applicable to any corresponding salicylic acid derivatives.

It has been discovered by this invention that specifically the N-alkylated salicylamides, such as N-octadecyl salicylamide, are capable of reacting with formaldehyde and secondary amines to form compounds which appear to be amino methylene derivatives. The resultant products are useful for many purposes and particularly, when converted to their salts, for imparting water repellency to textiles. The reactions whereby salicylic derivatives are prepared according to this invention probably take the following course:

R1 represents an aliphatic radicle, which maybe interrupted by ester, imido, imino and like linking groups; and which, in those cases where the final product is to be employed as a textile water repellent agent, preferably contains from 12 to 22 carbon atoms.

R2 represents hydrogen or an aliphatic radicle which may be interrupted by ester, amido,

ether, imino and like linking groups.

is.- Y., and Rolston Lyman assignors to National N. J., a cor- R3 in each occurrence, and independently of its other occurrence, represents an alkyl radicle containing up to 22 carbon atoms, which alkyl radicles, in those cases where the final product is to be employed as a textile water repellent agent, preferably containing from 1 to 4 carbon atoms.

n represents a whole number from 1 to 2.

salicylamides operative as starting materials in the process of this invention are in general those amides of salicylic acid containing an aliphatic radicle substituted in the amide nitrogen thereof. Examples'of salicylamides which are suitable as starting materials in the practice of this invention are the N-methyl, ethyl, -butyl, -capryl, -decyl, -1auryl, -myristyl, -palmity1, -margaryl, -stearyl, -0leyl, -arachidyl, -erucyl, and like salicylamides. Likewise, the di-N alkyl salicylamides may be employed, such as N-stearyl, N-methyl salicylamide, di-N propyl salicylamide, di-N stearyl salicylamide, and the like. The aliphatic radicle substituted in the amido nitrogen need not be a simple alkyl chain, but may be branched or interrupted by ester, amido, ether,

imino, etc., groups; for instance, the N-salicylamido, N-stearamido ethylene diamide would be suitable as a starting material in the process of this invention. Particularly where an aliphatic radicle substituted in the amido nitrogen of the salicylamide includes or consists of a higher fatty alkyl group containing from 12 to 22 carbon atoms, the acid salts and alkali phenates of the condensation products obtained therefrom in accordance with thisinvention are highly. efiicient agents for imparting permanent water repellency to textile fabrics. Instead of the pure salicylamides, there may, of course, be employed mixtures of salicylamides coming within the requirements above set forth, for instance, amides formed by interaction of salicylic acid with amines derived from the mixed fatty radicles contained in derived from petroleum fractions.

Amines which may be condensed with salicylamides and formaldehyde in accordance with this invention include any secondary alkylamines, such as dimethylamine, diethylamine, dipropyl amine, dibutyl amine, methyl decyl amine, methyl stearylamine distearylamine and the like. Preferably, in those cases where the ultimate con-' densation products are to be employed in textile treatment, these should be short chain secondary amines, containing alkyl radicles of not over 4 carbon atoms.

The condensation of this invention may be carried. out by mixing the selected N-aliphatic substituted salicylamide, formaldehyde and the selected amine, and heating the mixture at temperatures upwards of 40 C. and preferably upwards of C. for from 3 to 8 hours. The molecular proportions of the reactants supplied may be varied in accordance with the final products desired. If the reactants are supplied in aldehyde and amine may be separated by tion, all parts outlined are readily converted to salts and solubilized by dilute mineral and organic acids to give foamy; saponaceous solutions. Examples of suitable organic acids are formic, acetic, lactic, oxalic and like acids. Suitable mineral acids are hydrochloric, sulfuric, phosphoric, nitric and like acids. These acid salt compositions, preferably the salts produced by the action of organic acids.

are capable of combining with reactive textile fibers such as cellulosic fibers, silk and wool to impart water-repellency thereto, such treatments being carried out by impregnating the fibers with the condensation products of this invention and veloped cannot be baked wet without deteriorating the fabric. Likewise, byvirtue of the phenolic OH groups attached to the benzene nucleus in the compounds of this invent1on, these compounds are capable of reacting with strong alkalis, such as sodium, potassium, tetraethylammonium and like hydroxides, to form phenates which are soluble and/or dispersible in aqueous media. Such aquerecrystallization from benzene exhibited a melt-- ous preparations are highly effective agents for imparting water repellency to textiles, having no tendency to yellow textile fabrics as has been the experience with many water repellents of this general type heretofore employed. In addition to their usefulness for water proofing of textiles,

Following are examples for the preparation of condensation products according to this invengiven being by weight.

EXAMPLE I Diethylamino methylene N-octadecyl salicylamide An octadecyl salicylamide was prepared by mixing 54 parts (1 mol) of octadecylamine, .28 parts (1 mol) of salicylic acid and parts of pyridine and heating to C. untila homogeneous solu-'- tion resulted. 20 parts was separated from the washed and pressed dry.

213 parts (1 mol) of the octadecyl salicylamide produced as just described were dissolved in 40 parts (1 mol) of diethylamine and to this soluof phosphorus trichloridetion were added 46 parts (1 mol) of 37% of formaldehyde. The mixture was then refluxed at 60 C. for 5 hours. The resultant condensation product was insoluble in water but formed a soapy solution in dilute acetic acid. The solubilized product was found to be suitable for impregating textiles to impart water repellency thereto.

Exmrnn II Di (diethylamino methylene) Ill-octadecyl salicylamide N-octadecyl salicylamide was prepared by the reaction of salicylic amine. salicylamide were condensed with 11 parts (2 mols) of diethylamine and 8.3 parts (2 mols) of 37% formaldehyde at 60 C. for 6 hours. The product was a reddish viscous oil readily soluble in dilute organic and mineral acids such as EXAMPLE III Di (dimethylamino methylene) N-octadecyl salicylamide The diethylamine of Example II was replaced with 14 parts (2 mols) of 33% aqueous dimethylthe procedure of that example was a solid, I

ing range 6264 C. Analysis showed carbon 73.2%, hydrogen 11.0% (theory 73.9% and 11.4% respectively).

The product was readily soluble -EXAMPLE IV Diethylamino methylene N-tetradecyl salicylamide 1 To a solution of 33.5 parts (1 mol) of N-tetradecyl salicylamide in v100 in dilute acids.

then added with cooling and stirring. The resultant mixture was then refluxed at C. for 6 hours. The resultant product was a. waxy, brown solid soluble in dilute acids.

EXAMPLE V- I Diallylamz'no methylene N-tetmdecyl salicylamide parts (1 mol) of give a foamy, soapy solutio EXAMPLE VI Dietliylamino methylene N-octadeczfl salicylamide 39 parts (1 mol) of N-octadecyl-salicylamide and '7 parts (1 mol) of diethylamine were added to the solution. The solution was refluxed 6 hours at 80 C. The resultant condensation prodacid chloride with octadecyl- 20 parts (1 mol) of this N-octadecyl impaired in ous bath containing 0.1%

uct was readily soluble in dilute acids to give a foamy, soapy solution.

EXAMPLE V11 Dibuty laminomethylene N-octadecyl salicylamide cream.

EXAMPLE VIII Di (dimethylaminomethylene) N-di-octadecyl salicylamide 100 parts of di-n-octadecyl amine were dissolved in 200 parts of methyl ethyl ketone, and to the solution were added 27 parts of salicylic acid and 15.5 parts of pyridine. The solution was raised to reflux temperature and 29 parts of phosphorus trichloride added dropwise and with stirring. The reaction was refluxed thereafter 2% hours, then stirred into a hot (70-80") 25% solution of sulfuric acid. This was followed by washes with water, 20% sodium carbonate and water. The solvent was then removed and the intermediate, N-di-octadecyl salicylamide dissolved in 200 parts of 95% ethyl alcohol. To this were added 64 parts of 33% dimethylarnine solution and 38 parts of 37% formalin, and the resulting solution refluxed 18 hours. When the solvent was evaporated 154 parts of the product were obtained as a viscous paste which dispersed in dilute acetic acid solution to give a thick cream.

EXAMPLE IX Imparting water repellence to fabric by salts All of the products above described were found to be capable of reacting with textile fibers to impart water repellency thereto. As a specific example carried out upon the purified product of Example I, a solution in 10% acetic acid was prepared from this product. Cotton cloth was immersed in this solution, wrung out to an uptake of 100% of solution, based on the dry weight of the cloth, and immediately baked without preliminary drying at 150 C. 'for 6 minutes.

32 parts (1 mol) of di-n- The resultant cloth product was substantially um I strength and exhibited a very high degree of water repellency, which persisted after a number of washings.

EXAMPLE X Imparting water repellence to fabric by phenates 1 Parts Diethylaminomethylene N-octadecyl salicylamide (prepared as in Example I) Ethanol 10 Caustic soda solution (5% aqueous) An emulsion was prepared from the ingredients above listed by mixing the salicylamide and alcohol to form a paste, and thereafter slowly adding the caustic soda with high speed stirring. There resulted a creamy emulsion.

Cotton fabric was immersed in this emulsion,

removed, wrung out to an uptake of 100% of emulsion, based on the dry weight of the fabric,

and air dried. The dried fabric was baked at C. for 3 minutes, and then rinsed in'an aqueof di-dodecyl naphprovides novel dried, and was found to be highly water repellent which property persisted after numerous launderings. No yellowing or other adverse effect upon the color of the fabric was observed.

From the foregoing general discussion and detailed examples it will be seen that this invention salicylic derivatives having, inter alia, the properties of reacting with textile fibers to impart water repellency thereto. The products furthermore exhibit a high degree of surface activity, rendering them suitable as welting, penetrating, flotation, etc., agents. The raw ma terialsemployed in the production of ucts in accordance with this invention are the readily and cheaply procurable amines, formaldehyde and salicylic acid.

We therefore claim:

1. Process which comprises heating to condense an amide having the general form la:

CN A R: with formaldehyde and an amine having the formula:

in which formulae R1 represents an aliphatic radicle containing up to 22 carbon atoms; Ra represents a substituent chosen from the group consisting of hydrogen and a 'phatic radicles containing up to 22 carbon atoms; and R3 in each occurrence, and independently of its other occurrence, represents an alkyl radicle containing a up to 22 carbon atoms said reactants being present in the ratio of 1 mol of the amide to from 1-2 mols of formaldehyde and amine.

2. Process which comprises heating to condense N-octadecyl salicylamide with formaldehyde and with dimethylamine said reactants being present in the ratio of 1 mol of the amide to from 1-2 mols of formaldehyde and amine.

3. Process which comprises heating to condense N-tetradecyl salicylamide with formaldehyde and with diethylamine said reactants being present in the ratio of 1 mol of the amide to from 1-2 mols of formaldehyde and'amine.

4. Process which comprises heating to condense di-N-octadecyl salicylamide with formaldehyde and with diethylamine said reactants being present in the ratio of 1 mol of the amide to from 1-2 mols of formaldehyde and amine.

' 5. A substance chosen from the group consisting of compounds having the general formula:

Ho H R:

I LI Rs II 22 carbon atoms; R3 in each occurrence, and independently of its other occurrence,

represents an. alkyl radicle containing up to 22 carbon atoms; n-represents a whole number from 1 to 2;

and salts and phenates thereof.

6. A water-repellency imparting agent for textiles comprising substance chosen from the group these prodsubstituent consisting of salts and having the general formula:

wherein R1 represents an alkyl radicle containing from 12 to 22 carbon atoms; R2 represents a independently of any other occurrence, represents an alkyl radicle containing up to 4 carbon a,ses,e4o phenates of compounds 8. A substance chosen from the group conslsting or salts and phenates of 'dlethyiamino methylene N-tetradecyl sallcylamide.

9. A substance chosen methylene d1 N-octadecyl salicylamlde.

DONALD PRICE, ROLSTON LYMAN BOND.

and n represents a whole number from of salts and phenates of dimethylamino from the group consisting or salts and phenates o1 diethylamino 

